Semiconductor device and manufacturing method thereof

ABSTRACT

A method includes forming a mask layer above a substrate. The substrate is patterned by using the mask layer as a mask to form a trench in the substrate. An isolation structure is formed in the trench, including feeding first precursors to the substrate. A bias is applied to the substrate after feeding the first precursors. With the bias turned on, second precursors are fed to the substrate. Feeding the first precursors, applying the bias, and feeding the second precursors are repeated.

PRIORITY CLAIM AND CROSS-REFERENCE

This present application is a divisional application of U.S. patentapplication Ser. No. 16/837,580, filed Apr. 1, 2020, which is hereinincorporated by reference in its entirety.

BACKGROUND

The semiconductor integrated circuit (IC) industry has experienced rapidgrowth. In the course of IC evolution, functional density (i.e., thenumber of interconnected devices per chip area) has increased whilegeometry size (i.e., the smallest component (or line) that can becreated using a fabrication process) has decreased. This scaling downprocess increases production efficiency and lowers associated costs.

Such scaling down has also increased the complexity of processing andmanufacturing ICs and, for these advances to be realized, similardevelopments in IC processing and manufacturing are desired. Forexample, a three dimensional transistor, such as a fin-like field-effecttransistor (FinFET), has been introduced to replace a planar transistor.

BRIEF DESCRIPTION OF THE DRAWINGS

Aspects of the present disclosure are best understood from the followingdetailed description when read with the accompanying figures. It isnoted that, in accordance with the standard practice in the industry,various features are not drawn to scale. In fact, the dimensions of thevarious features may be arbitrarily increased or reduced for clarity ofdiscussion.

FIGS. 1A-1E are perspective views of a method for manufacturing asemiconductor structure at various stages in accordance with someembodiments of the present disclosure.

FIG. 2 is a flow chart of a method of a bias-induced selectively ALDprocess in accordance with some embodiments of the present disclosure.

FIG. 3 is a schematic diagram of a fabrication apparatus according tosome embodiments of the present disclosure.

FIGS. 4A-4E are cross-sectional views taking along line A-A of FIG. 1Cat various stages in accordance with some embodiments of the presentdisclosure.

FIG. 5 is a timing diagram of bias pulses and precursors providingaccording to some embodiments.

FIGS. 6A-6E are cross-sectional views taking along line A-A of FIG. 1Cat various stages in accordance with some embodiments of the presentdisclosure.

FIG. 7 is a flow chart of a method of a bias-induced selectively ALDprocess in accordance with some embodiments of the present disclosure.

FIGS. 8A-8E are cross-sectional views taking along line A-A of FIG. 1Cat various stages in accordance with some embodiments of the presentdisclosure.

FIG. 9 is a timing diagram of bias pulses and precursors providingaccording to some embodiments.

FIGS. 10A-10I are perspective views of a method for manufacturing asemiconductor device at various stages in accordance with someembodiments of the present disclosure.

FIGS. 11A-11F are cross-sectional views taking along line B-B of FIG.10F at various stages in accordance with some embodiments of the presentdisclosure.

FIGS. 12A-12F are cross-sectional views taking along line B-B of FIG.10F at various stages in accordance with some embodiments of the presentdisclosure.

FIGS. 13A-13F are cross-sectional views taking along line B-B of FIG.10F at various stages in accordance with some embodiments of the presentdisclosure.

FIG. 14 is a perspective view of a semiconductor device according tosome embodiments.

FIGS. 15A-15K are cross-sectional views of a method for manufacturing asemiconductor structure at various stages in accordance with someembodiments of the present disclosure.

FIGS. 16A-16G are cross-sectional views a method for manufacturing asemiconductor structure at various stages in accordance with someembodiments of the present disclosure.

DETAILED DESCRIPTION

The following disclosure provides many different embodiments, orexamples, for implementing different features of the provided subjectmatter. Specific examples of components and arrangements are describedbelow to simplify the present disclosure. These are, of course, merelyexamples and are not intended to be limiting. For example, the formationof a first feature over or on a second feature in the description thatfollows may include embodiments in which the first and second featuresare formed in direct contact, and may also include embodiments in whichadditional features may be formed between the first and second features,such that the first and second features may not be in direct contact. Inaddition, the present disclosure may repeat reference numerals and/orletters in the various examples. This repetition is for the purpose ofsimplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed.

Further, spatially relative terms, such as “beneath,” “below,” “lower,”“above,” “upper” and the like, may be used herein for ease ofdescription to describe one element or feature's relationship to anotherelement(s) or feature(s) as illustrated in the figures. The spatiallyrelative terms are intended to encompass different orientations of thedevice in use or operation in addition to the orientation depicted inthe figures. The apparatus may be otherwise oriented (rotated 90 degreesor at other orientations) and the spatially relative descriptors usedherein may likewise be interpreted accordingly.

As used herein, “around”, “about”, “approximately”, or “substantially”shall generally mean within 20 percent, or within 10 percent, or within5 percent of a given value or range. Numerical quantities given hereinare approximate, meaning that the term “around”, “about”,“approximately”, or “substantially” can be inferred if not expresslystated.

The fins may be patterned by any suitable method. For example, the finsmay be patterned using one or more photolithography processes, includingdouble-patterning or multi-patterning processes. Generally,double-patterning or multi-patterning processes combine photolithographyand self-aligned processes, allowing patterns to be created that have,for example, pitches smaller than what is otherwise obtainable using asingle, direct photolithography process. For example, in one embodiment,a sacrificial layer is formed over a substrate and patterned using aphotolithography process. Spacers are formed alongside the patternedsacrificial layer using a self-aligned process. The sacrificial layer isthen removed, and the remaining spacers may then be used to pattern thefins.

Embodiments of the present disclosure relate to semiconductor structuresand methods for forming semiconductor structures by performingbias-induced selective atomic layer deposition (ALD) processes. Theseembodiments are discussed below in the context of forming finFETtransistors having a single fin or multiple fins on a bulk siliconsubstrate.

FIGS. 1A-1E are perspective views of a method for manufacturing asemiconductor structure at various stages in accordance with someembodiments of the present disclosure. In some embodiments, thesemiconductor structure shown in FIGS. 1A-1E may be intermediate devicesfabricated during processing of an integrated circuit (IC), or a portionthereof, that may include static random access memory (SRAM), logiccircuits, passive components, such as resistors, capacitors, andinductors, and/or active components, such as p-type field effecttransistors (PFETs), n-type FETs (NFETs), multi-gate FETs, metal-oxidesemiconductor field effect transistors (MOSFETs), complementarymetal-oxide semiconductor (CMOS) transistors, bipolar transistors, highvoltage transistors, high frequency transistors, other memory cells, andcombinations thereof.

Reference is made to FIG. 1A. A substrate 110 is provided. The substrate110 includes an n-type region 100 n and a p-type region 100 p. N-typedevices (such as NFETs) will be formed on the n-type region 100 n, andp-type devices (such as PFETs) will be formed on the p-type region 100p. In some embodiments, the substrate 110 may include silicon (Si).Alternatively, the substrate 110 may include germanium (Ge), silicongermanium, gallium arsenide (GaAs), or other appropriate semiconductormaterials. In some alternative embodiments, the substrate 110 mayinclude an epitaxial layer. Furthermore, the substrate 110 may include asemiconductor-on-insulator (SOI) structure having a buried dielectriclayer therein. The buried dielectric layer may be, for example, a buriedoxide (BOX) layer. The SOI structure may be formed by a method referredto as separation by implantation of oxygen (SIMOX) technology, waferbonding, selective epitaxial growth (SEG), or other appropriate method.

A mask layer 120 (may be a hard mask layer) is formed over the topsurface 112 of the substrate 110. In some embodiments, the mask layer120 includes nitride. For example, the mask layer 120 is made of siliconnitride (SiN). However, other materials, such as SiON, silicon carbide,or combinations thereof, may also be used. The mask layer 120 may beformed by a process such as chemical vapor deposition (CVD), plasmaenhanced chemical vapor deposition (PECVD), or low pressure chemicalvapor deposition (LPCVD). Alternatively, the mask layer 120 may be madeof a silicon oxide and then converted to SiN by nitridation.

In some embodiments, a pad layer 130 is formed over the top surface 112of the substrate 110 and between the mask layer 120 and the substrate110. The pad layer 130 protects the top surface 112 from direct contactwith the mask layer 120. For example, the pad layer 130 can protectactive regions formed in the substrate 110. The active regions are usedfor forming devices (such as transistors, resistors, etc.). Dependingupon the devices to be formed, the active regions may include either ann-well or a p-well as determined by the design conditions. In someembodiments, the pad layer 130 is made of a thermal oxide. Once formed,the mask layer 120 and the pad layer 130 are patterned through suitablephotolithographic and etching processes to form openings 132 over thetop surface 112.

Reference is made to FIG. 1B. The exposed portions of the substrate 110through the openings 132 (see FIG. 1A) are removed by an etchingprocess, such as reactive ion etching (RIE), in order to form thetrenches 114 in the substrate 110. In some embodiments, the substrate110 is etched to form semiconductor fins 116, and the trenches 114 areconfigured to separate adjacent two semiconductor fins 116. In otherwords, one of the semiconductor fins 116 is between adjacent two of thetrenches 114.

Reference is made to FIG. 1C. Isolation materials 140′ are selectivelyformed in the trenches 114. The isolation materials 140′ are formed byperforming a bias-induced selectively ALD process, as described ingreater detail below. Atomic layer deposition (ALD) is an approach tofilling dielectrics that involves depositing a monolayer of precursorover the substrate 110, purging the chamber, and introducing a reactantthat reacts with the precursor to leave a monolayer of product. Thecycle can be repeated many times to build a layer with a sufficientthickness to be functional. The thickness of the deposition layer isdetermined by the deposition cycles of the ALD processes.

FIG. 2 is a flow chart of a method M1 of a bias-induced selectively ALDprocess in accordance with some embodiments of the present disclosure.FIG. 3 is a schematic diagram of a fabrication apparatus 200, accordingto some embodiments of the present disclosure. FIGS. 4A-4E arecross-sectional views taking along line A-A of FIG. 1C at various stagesin accordance with some embodiments of the present disclosure. In someembodiments, the isolation material 140′ in FIG. 1C is formed in thefabrication apparatus 200 of FIG. 3. It is noted that the sizes of theprecursors shown in FIGS. 4B-4D are illustrated only, and do not limitthe scope of the embodiments.

Reference is made to FIGS. 2, 3, and 4A. In operation S12 of the methodM1, a wafer is positioned on a chuck of a fabrication apparatus. Forexample, the wafer (e.g., the structure in FIG. 1B) is positioned on achuck 220 of the fabrication apparatus 200. In some embodiments, thefabrication apparatus 200 includes a chamber 210, the chuck 220, aplasma source 230, and a precursor delivery 240. The chuck 220 is in thechamber 210, and the plasma source 230 and the precursor delivery 240are connected to the chamber 210.

The plasma source 230 may be a remote plasma system which is separatedfrom the chamber 210. Treatment gases and carrier gases may beintroduced into the plasma source 230 and the treatment gases areexcited to create reaction gases containing plasma. The reaction gasesare reactive species of plasmarized ions. In some embodiments, thetreatment gases are exited using microwaves to create the reaction gascontaining plasma. The microwaves are generated using a microwaveoscillator and are introduced into the plasma source 230 using anoptical waveguide. The reaction gases are then fed through a conduitinto the chamber 210.

In some embodiments, the fabrication apparatus 200 further includes aturbo pump 250 and a pressure controller 260 (e.g., automatic pressurecontroller (APC)). The turbo pump 250 is connected to the chamber 210through the pressure controller 260. In some embodiments, when the waferis positioned in the chamber 210, a vacuum is applied to the chamber 210by the turbo pump 250 to remove oxygen and moisture. The pressurecontroller 260 is configured to control the pressure inside the chamber210. In some embodiments, when the wafer is positioned in the chamber210, the temperature is raised to an acceptable level that is suitablefor the ALD deposition before the operation S14.

In operation S14 of the method M1, a bias is applied to the chuck. Thebias may be a DC bias and/or a radio-frequency (RF) bias. For example,an RF bias is applied to the chuck 220 in the case of FIG. 4A. With theRF bias, since the mask layer 120 (e.g., a dielectric layer) has anelectrical conductivity lower than that of the substrate 110 (e.g., asemiconductor material), charges (i.e., electrons in this case) are lessmovable within the mask layer 120, such that more charges remain in thevicinity of the surface of the mask layer 120 as shown in FIG. 4A.Moreover, since the electrons are lighter than ions, the electrons areeasier to accumulate in the vicinity of the surface of the mask layer120.

In some embodiments, the fabrication apparatus 200 further includes abias source 270 connected to the chuck 220 as shown in FIG. 3. The biassource 270 is configured to apply a bias to the chuck 220 and thus tothe wafer positioned thereon. In some embodiments, the bias source 270is configured to apply DC and/or RF bias to the chuck 220. In someembodiments, the bias source 270 is configured to apply positive ornegative DC bias to the chuck 220 to accelerate or decelerate thedeposition rate of the selective ALD process. In some embodiments, thebias may have a power greater than about 0 W and equal to or less thanabout 50 W, e.g., about 20 W. If the power is greater than about 50 W,the gases (e.g., the precursors/processing gases) in the chamber 210 maybe ionized to form plasma, which may bombard the wafer to damage thestructure formed thereon. In some embodiments, the bias is an RF bias,and the frequency range thereof is in a range of about 3 kHz to about300 GHz.

FIG. 5 is a timing diagram of bias pulses and precursors providingaccording to some embodiments. Reference is made to FIGS. 3, 4A, and 5.In FIG. 5, the bias applied to the chuck 220 continues a first periodT1. The bias is applied before precursors are fed into the chamber 210.Once the RF bias is applied to the chuck 220, electrons move to thesurface of the mask layer 120. Hence, the surface of the mask layer 120is negative charged in this case.

In operation S16 of the method M1, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and4B. For example, first precursors P1 (e.g., H₂O in this case) are fedinto the chamber 210 from the precursor delivery 240. As shown in FIG.4B, each of the H₂O molecules is a polar molecule and has a slightnegative charge near its oxygen atom and a slight positive charge nearits hydrogen atoms. The negative charges (electrons) in the vicinity ofthe surface of the mask layer 120 repulse the H₂O molecules due to theirpartial negative charges (oxygen). The H₂O molecules may be mostlyattracted by the substrate 110, and thus are mostly deposited on thesubstrate 110 rather than on the mask layer 120. Stated differently,more H₂O molecules are deposited on the substrate 110 than on the masklayer 120. As shown in FIG. 4C, the H₂O molecules are mostly absorbed onthe surface 112 of the substrate 110. In some embodiments, there arestill some H₂O molecules absorbed on the surfaces of the dielectricmaterials (i.e., the mask layer 120 and the pad layer 130 in this case).

Reference is made to timing diagram of FIG. 5. After the bias applied tothe chuck 220 is turned on and before the bias is turned off, the firstprecursors P1 are fed into the chamber 210 for a second period T2. Insome embodiments, the second period T2 is shorter than the first periodT1 by multiple times. For example, the first period T1 may be ten ormore times the second period T2. Further, the bias is turned off afterthe feeding of the first precursor P1 is stopped. A third period T3 isbetween the beginning of the bias supply and the beginning of the firstprecursor feeding, and a fourth period T4 is between the finish of thefirst precursor feeding (i.e., stopping the first precursor feeding) andthe finish of the bias supply (i.e., turning off of the bias supply). Insome embodiments, the third period T3 is long enough to charge the masklayer 120, and the fourth period T4 is long enough to provide thereaction time of the first precursor deposition.

Reference is made to FIGS. 3 and 4B. In some embodiments, when the firstprecursors P1 are fed into the chamber 210, the pressure in the chamber210 may be changed. The varied pressure may disturb the chargedistribution on the chuck 220. The pressure controller 260 is configuredto maintain the pressure at a predetermined value of range. With thisconfiguration, the pressure in the chamber 210 is well controlled, andthe charge distribution caused by the bias applied in operation S14 canmaintain in a substantially steady state. Stated in another way, thepressure controller 260 prevents the charge distribution from beingdisturbed when the first precursors P1 are fed into the chamber 210.

In some embodiments, during the operations S14 and S16, the plasmasource 230 is turned off, such that there is no or negligible plasma inthe chamber 210 when the bias is applied to the chuck 220. In some otherembodiments, the first precursors P1 is plasma, and the first precursorsP1 are fed into the chamber 210 from the plasma source 230. During thisprocess, the plasma is originated from the plasma source 230 and not inthe chamber 210, such that a bias with a low power can be applied to thechuck 220 to perform the selective ALD process, because the bias appliedto the chuck 220 is irrelevant to the generation of plasma.

In operation S18 of the method M1, the bias is turned off, and infollowing operation S20 of the method M1, the excess first precursorsare purged out of the chamber. Specifically, some of the firstprecursors P1 are absorbed to the surface 112 of the substrate 110during the periods T2 and T4 (see FIG. 5). After the fourth period T4,the bias is turned off, such that the electrons in the vicinity of thesurface of the mask layer 120 are gradually disappeared. Then, purginggases such as inert gases (Ar or N₂), which are substantially free fromoxygen and moisture (for example, less than about 1 volume percent, lessthan about 0.1 percent, about 0.01 percent, about 0.001 percent, orlower), enter the chamber 210 to purge the excess first precursors P1,which are not absorbed on the substrate 110, the mask layer 120, and thepad layer 130, out of the chamber 210.

In some embodiments, the fabrication apparatus 200 in FIG. 3 furtherincludes a rotary pump 280 and a valve (e.g., stop valve) 285. Therotary pump 280 is connected to the chamber 210 via the valve 285, andthe rotary pump 280 is configured to pump out the purging gases and theexcess first precursors P1 in the chamber 210 when the pressurecontroller 260 is turned off. In some other embodiments, the turbo pump250 may pump out the purging gases and the excess first precursors P1 inthe chamber 210 when the pressure controller 260 is turned on. In someembodiments, the fabrication apparatus 200 in FIG. 3 further includes afilter (e.g., trap filter) 290 connected to the chamber 210, the valve285, and the pressure controller 260. The filter 290 is configured totrap the gases (e.g., the purging gases and/or precursors) and preventthe gases reflected toward the chamber 210.

In operation S22 of the method M1, second precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and4D. For example, second precursors P2 (e.g., silicon precursors in thiscase) are fed into the chamber 210 from the precursor delivery 240. Asshown in FIG. 4D, the second precursors P2 are attracted by the firstprecursors absorbed on the substrate 110 (—OH in this case). The secondprecursors P2 are likely to be attracted by —OH, and thus more secondprecursors P2 are deposited on the surface 112 of the substrate 110 andless second precursors P2 are deposited on the surfaces of the masklayer 120 and the pad layer 130. As shown in FIG. 4E, a dielectric film140″ is formed on the surfaces of the substrate 110, the mask layer 120,and the pad layer 130.

In FIG. 4E, a portion of the dielectric film 140″ in contact with thesubstrate 110 is denser than another portion of the dielectric film 140″in contact with the mask layer 120. For example, most area of thesurfaces of the mask layer 120 may be exposed by the dielectric film140″ while most area of the surface 112 of the substrate 110 is coveredby the dielectric film 140″. Therefore, a bias-induced selective ALDprocess is performed to selectively deposit a dielectric film 140″ onthe substrate 110 at a faster deposition rate than on the mask layer 120and the pad layer 130. In some embodiments, the dielectric film 140″ isa monolayer.

In some embodiments, the dielectric film 140″ may be asilicon-containing layer, such as SiO₂. In this case, the secondprecursors P2 may be (3-Aminopropyl)triethoxy silane,N-sec-Butyl(trimethylsilyl)amine, Tris(dimethylamino)silane (TDMAS),Tetraethyl orthosilicate (TEOS), SiCl₄, Tris(tert-butoxy)silanol(TBS),Tris(tert-pentoxy)silano(TPS), or other suitable materials. In someother embodiments, the dielectric film 140″ may include other suitablematerials (such as high-k materials).

In FIG. 5, the purging of the second precursors P2 maintains for a fifthperiod T5. In some embodiments, a sixth period T6 is between the periodsT4 and T5. In some embodiments, the sixth period T6 is for neutralizingthe surface of the mask layer 120. Moreover, a seventh period T7 isbetween the fifth period T5 and the next first period T1. In someembodiments, the seventh period T7 provides the reaction time of thesecond precursor deposition.

In operation S24 of the method M1, the excess second precursors arepurged out of the chamber. Specifically, the second precursors P2 aremostly absorbed to the surface 112 of the substrate 110 during theperiods T5 and T7 (see FIG. 5). After the fifth period T5, purging gasessuch as inert gases (Ar or N₂) enter the chamber 210 again to purge theexcess second precursors P2 out of the chamber 210.

After the operation S24, the dielectric film 140″ is mostly formed onthe surface 112 of the substrate 110 as shown in FIG. 4E, and thisdielectric film 140″ may expose portions of the surfaces of the masklayer 120 (and the pad layer 130). That is, the selective ALD depositionprocess results in no or negligible dielectric film 140″ deposited onthe mask layer 120 and the pad layer 130. For example, the dielectricfilm 140″ unintentionally deposited on the mask layer 120 and the padlayer 130 may have a thinner thickness than that deposited on thesubstrate 110. Then, the method M1 goes to the operation S14 to repeatthe operations S14-S24 and form another dielectric film on thedielectric film 140″. The cycle of the operations S14-S24 may berepeated many times to form the isolation materials 140′ in the trenches114, as shown in FIG. 1C.

In operation S26 of the method M1, the wafer is taken out of thechamber. Specifically, after the bias-induced selective ALD process(i.e., the isolation materials 140′ are filled in the trenches 114 inthis case), the deposition process is finished, and the wafer is takenout of the chamber (e.g., loaded out of the chamber, by using one ormore robotic arms, to a wafer cassette placed on a load port of thechamber) to process the next manufacturing process.

Reference is made to FIG. 1D. A planarization process is performed toremove the mask layer 120, the pad layer 130, and the isolationmaterials 140′ outside the trench 114, such that the semiconductor fins116 are exposed. In some embodiments, the planarization process is achemical-mechanical polishing (CMP) process. In some embodiments, theCMP process is omitted, as long as the selective ALD process is wellcontrolled to result in no isolation material 140′ deposited on the masklayer 120. In such scenarios, an additional etching process may beoptionally performed to remove the mask layer 120 and the pad layer 130from the fins 116.

Reference is made to FIG. 1E. The isolation materials 140′ of FIG. 1Dare recessed to form isolation structures 140 adjacent to and in contactwith the semiconductor fins 116, and portions of the semiconductor fins116 protrude from the isolation structures 140. In following steps,front-end-of-line (FEOL) processes continue to form source/drain regions(e.g., n-doped or p-doped epitaxy structures, n-doped or p-dopedimplanted regions or the like), gate dielectric layers and gateelectrodes on the semiconductor fins 116 to complete fabrication ofFinFETs, and back-end-of-line (BEOL) processes follow the FEOL processesto form metal contacts, metal vias and metal lines over the FinFETs tocomplete fabrication of integrated circuits (ICs).

In FIG. 1C, the isolation material 140′ is formed by performing thebias-induced selective ALD process. By providing a bias on the chuck220, the charges have different distributions in different materials.The charges may attract or repulse the precursors to increase ordecrease the corresponding deposition rate. In some other embodiments,the planarization process shown in FIG. 1D can be omitted when there isa high deposition selectivity between the dielectric layer (i.e., themask layer 120) and the semiconductor layer (i.e., the substrate 110).Furthermore, a self-aligned monolayers (SAMs), which may formed using anadditional deposition process and cause defect issues, can be omitted tosimplify the manufacturing process.

The isolation materials 140′ in FIG. 1C may be formed using other biasand/or precursors. FIGS. 6A-6E are cross-sectional views taking alongline A-A of FIG. 1C at various stages in accordance with someembodiments of the present disclosure. Throughout the various views andillustrative embodiments, like reference numbers are used to designatelike elements. The present embodiment may repeat reference numeralsand/or letters used in FIGS. 4A-4E. This repetition is for the purposeof simplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed. In thefollowing embodiments, the structural and material details describedbefore are not repeated hereinafter, and only further information issupplied to perform the semiconductor devices of FIGS. 6A-6E. In someembodiments, the formation of the isolation material 140′ in FIGS. 6A-6Eis performed in the fabrication apparatus 200 of FIG. 3 and/or using themethod M1 in FIG. 2. In some embodiments, the time table of FIG. 5 isalso applied to the manufacturing processes in FIGS. 6A-6E. It is notedthat the sizes of the precursors shown in FIGS. 6A-6D are illustratedonly, and do not limit the scope of the embodiments.

Reference is made to FIGS. 2, 3, and 6A. In operation S12 of the methodM1, a wafer is positioned on a chuck of a fabrication apparatus. In someembodiments, the surfaces of the structure (i.e., the substrate 110 andthe mask layer 120) may be terminated with terminating species TS. Insome examples, the terminating species TS is hydroxide (—OH), oxygen(—O), or the like. Termination by hydroxide (—OH) and/or oxygen (—O) canoccur, for example, as a result of a cleaning or photoresist strippingprocess performed on the surfaces of the substrate 110 and the masklayer 120 and/or by exposing the surfaces of the substrate 110 and themask layer 120 to a natural environment that contains oxygen. Theterminating species TS can be other species, such as hydrogen (—H),nitrogen (—N), ammonia (—NH₃), or the like, such as depending on acleaning and/or stripping process that is performed on the surfaces. Insome embodiments, the surfaces of the substrate 110 and the mask layer120 initially carries the terminating species TS. That is, the substrate110 and the mask layer 120 includes terminating species TS itself. Insome other embodiments, the surfaces of the substrate 110 and the masklayer 120 are initially neutral, and a surface treatment (e.g., thecleaning and/or stripping process mentioned above) can be performed onthe surfaces to change or modify the surface termination. In still someother embodiments, H₂O are fed into the chamber 210 to form theterminating species TS on the surfaces of the substrate 110.

In operation S14 of the method M1, a bias is applied to the chuck. Thebias is a negative DC bias in the case of FIG. 6A. With the negative DCbias, since the substrate 110 (e.g., a semiconductor material) has anelectrical conductivity higher than that of the mask layer 120 (e.g., adielectric layer), charges (i.e., electrons in this case) areaccumulated within the substrate 110, such that more charges remain inthe vicinity of the surface of the substrate 110 as shown in FIG. 6A.The bias source 270 in FIG. 3 is configured to apply the negative DCbias to the chuck 220, and the bias may have a power greater than about0 W and equal to or less than about 50 W, e.g., about 20 W.

In some embodiments, the bias applied to the chuck 220 continues thefirst period T1 as shown in FIG. 5. The bias is applied beforeprecursors are fed into the chamber 210. Once the negative DC bias isapplied to the chuck 220, electrons move to the surface of the substrate110. Hence, the surface of the substrate 110 is negative charged in thiscase.

In operation S16 of the method M1, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and6B. For example, first precursors P1′ (e.g., silicon precursors in thiscase) are fed into the chamber 210 from the precursor delivery 240. Insome embodiments, by controlling the temperature of the chamber 210and/or feeding reaction gases into the chamber 210, a chemical reactionoccurs such that a substituent is removed from the first precursor P1′,and thus the first precursors P1′ become partially positive. The firstprecursors P1′ with partial positive charges are mostly attracted by thesubstrate 110, and thus are mostly deposited on the substrate 110 ratherthan on the mask layer 120. As shown in FIG. 6C, the first precursorsP1′ are mostly absorbed on the surface 112 of the substrate 110. In someembodiments, there are still some first precursors P1′ absorbed on thesurfaces of the dielectric materials (i.e., the mask layer 120 and thepad layer 130 in this case).

The first precursors P1′ are fed into the chamber 210 for the secondperiod T2 (see FIG. 5). In some embodiments, the third period T3 in FIG.5 is long enough to charge the mask layer 120, and the fourth period T4in FIG. 5 is long enough to provide the reaction time of the firstprecursor deposition. Further, during the operations S14 and S16, theplasma source 230 is turned off, such that there is no or negligibleplasma in the chamber 210 when the bias is applied to the chuck 220. Insome other embodiments, the first precursors P1′ is plasma, and thefirst precursors P1′ are fed into the chamber 210 from the plasma source230. During this process, the plasma is originated from the plasmasource 230 and not in the chamber 210, such that a bias with a low powercan be applied to the chuck 220 to perform the selective ALD process.

In operation S18 of the method M1, the bias is turned off, and inoperation S20 of the method M1, the excess first precursors are purgedout of the chamber. In operation S22 of the method M1, second precursorsare fed into the chamber of the fabrication apparatus. Reference is madeto FIGS. 3 and 6D. For example, second precursors P2′ (e.g., oxidizerssuch as H₂O vapor, O₃, or O₂ plasma in this case) are fed into thechamber 210 from the precursor delivery 240 or the plasma source 230(for the O₂ plasma oxidizers). As shown in FIG. 6D, the secondprecursors P2′ are attracted by the first precursors absorbed on thesubstrate 110. The second precursors P2′ are likely to be attracted bythe first precursors, and thus more second precursors P2′ are depositedon the surfaces of the substrate 110 and less second precursors P2′ aredeposited on the surfaces of the mask layer 120 and the pad layer 130.As shown in FIG. 6E, a dielectric film 140″ is formed on the surfaces ofthe substrate 110, the mask layer 120, and the pad layer 130.

In FIG. 5, the purging of the second precursors P2′ maintains for thefifth period T5. In some embodiments, the sixth period T6 of FIG. 5 isfor neutralizing the surface 112 of the substrate 110. In someembodiments, the seventh period T7 of FIG. 5 provides the reaction timeof the second precursor deposition.

In operation S24 of the method M1, the excess second precursors arepurged out of the chamber. After the operation S24, a dielectric film140″ is mostly formed on the surface of the substrate 110 as shown inFIG. 6E, and this dielectric film 140″ may expose portions of thesurfaces of the mask layer 120 (and the pad layer 130). That is, theselective ALD deposition process results in no or negligible dielectricfilm 140″ deposited on the mask layer 120 and the pad layer 130. Then,the method M1 goes to the operation S14 to repeat the operations S14-S24and form another dielectric film on the dielectric film 140″. The cycleof the operations S14-S24 may be repeated many times to form theisolation materials 140′ in the trenches 114, as shown in FIG. 1C. Inoperation S26 of the method M1, the wafer is taken out of the chamber toprocess the next manufacturing process.

FIG. 7 is a flow chart of a method M2 of a bias-induced selectively ALDprocess in accordance with some embodiments of the present disclosure.FIGS. 8A-8E are cross-sectional views taking along line A-A of FIG. 1Cat various stages in accordance with some embodiments of the presentdisclosure. Throughout the various views and illustrative embodiments,like reference numbers are used to designate like elements. The presentembodiment may repeat reference numerals and/or letters used in FIGS.4A-4E. This repetition is for the purpose of simplicity and clarity anddoes not in itself dictate a relationship between the variousembodiments and/or configurations discussed. In the followingembodiments, the structural and material details described before arenot repeated hereinafter, and only further information is supplied toperform the semiconductor devices of FIGS. 8A-8E. In some embodiments,the formation of the isolation material 140′ in FIGS. 8A-8E is performedin the fabrication apparatus 200 of FIG. 3. It is noted that the sizesof the precursors shown in FIGS. 8A-8D are illustrated only, and do notlimit the scope of the embodiments.

Reference is made to FIGS. 3, 7, and 8A. In operation S12 of the methodM2, a wafer is positioned on a chuck of a fabrication apparatus. In someembodiments, the surfaces of the structure (i.e., the substrate 110 andthe mask layer 120) may be terminated with terminating species TS. Inoperation S16 of the method M2, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and8A. For example, first precursors P1′ (e.g., silicon precursors in thiscase) are fed into the chamber 210 from the precursor delivery 240. Thefirst precursors P1′ are absorbed both on the surfaces of the substrate110 and the mask layer 120 as shown in FIG. 8B.

FIG. 9 is a timing diagram of bias pulses and precursors providingaccording to some embodiments. Reference is made to FIGS. 3, 8A, and 9.In FIG. 9, the first precursors P1′ are fed into the chamber 210 for aneighth period T8. In some embodiments, during the operation S16, theplasma source 230 is turned off, such that there is no or negligibleplasma in the chamber 210 when the first precursors P1′ are fed into thechamber 210. In some other embodiments, the first precursors P1 isplasma, and the first precursors P1 are fed into the chamber 210 fromthe plasma source 230. In some embodiments, the ninth period T9 in FIG.9 is long enough to provide the reaction time of the first precursordeposition.

In operation S20 of the method M2, the excess first precursors arepurged out of the chamber, leaving first precursors absorbed on thesurfaces of the substrate 110 and the mask layer 120 as shown in FIG.8B. In operation S14 of the method M2, a bias is applied to the chuck.The bias is a positive DC bias in the case of FIG. 8C. With the positiveDC bias, since the substrate 110 (e.g., a semiconductor material) has anelectrical conductivity higher than that of the mask layer 120 (e.g., adielectric layer), charges (i.e., holes in this case) are accumulatedwithin the substrate 110, such that more charges remain in the vicinityof the surface of the substrate 110 as shown in FIG. 8C. The bias source270 in FIG. 3 is configured to apply the positive DC bias to the chuck220, and the bias may have a power greater than 0 W and equal to or lessthan about 50 W, e.g., about 20 W.

In some embodiments, the bias applied to the chuck 220 continues a tenthperiod T10 as shown in FIG. 9. The bias is applied before the secondprecursors P2′ (see FIG. 8D) are fed into the chamber 210. Once thepositive DC bias is applied to the chuck 220, electron holes move to thesurface 112 of the substrate 110. Hence, the surface 112 of thesubstrate 110 is positive charged in this case.

In operation S22 of the method M2, second precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and8D. For example, second precursors P2′ (e.g., H₂O in this case) are fedinto the chamber 210 from the precursor delivery 240. The positivecharges (holes) in the vicinity of the surface of the substrate 110attracts the H₂O molecules due to their partial negative charges(oxygen). The H₂O molecules may be mostly attracted by the substrate110, and thus are mostly deposited on the substrate 110 rather than onthe mask layer 120. As shown in FIG. 8E, the H₂O molecules are mostlyabsorbed on the surface 112 of the substrate 110 to form the dielectricfilm 140″. In some embodiments, there are still some H₂O molecules areabsorbed on the surfaces of the dielectric materials (i.e., the masklayer 120 and the pad layer 130 in this case).

Reference is made to FIG. 9. After the bias applied to the chuck 220 isturned on and before the bias is turned off, the second precursors P2′are fed into the chamber 210 for an eleventh period T11. In someembodiments, the eleventh period T11 is shorter than the tenth periodT10 by multiple times. Further, the bias is turned off after the feedingof the second precursor P2′ is stopped. A twelfth period T12 is betweenthe beginning of the bias supply and the beginning of the secondprecursor feeding, and a thirteenth period T13 is between the finish ofthe second precursor feeding and the finish of the bias supply. In someembodiments, the twelfth period T12 is long enough to charge thesubstrate 110, and the thirteenth period T13 is long enough to providethe reaction time of the second precursor deposition.

In operation S18 of the method M2, the bias is turned off, and inoperation S24 of the method M2, the excess second precursors are purgedout of the chamber. After the operation S24, a dielectric film 140″ ismostly formed on the surface 112 of the substrate 110 as shown in FIG.8E, and this dielectric film 140″ may expose portions of the surfaces ofthe mask layer 120 (and the pad layer 130). That is, the dielectric film140″ is not or barely deposited on the mask layer 120 and the pad layer130. Then, the method M2 goes to the operation S16 to repeat theoperations S16-S24 and form another dielectric film on the dielectricfilm 140″. The cycle of the operations S16-S24 may be repeated manytimes to form the isolation materials 140′ in the trenches 114, as shownin FIG. 1C. In operation S26 of the method M2, the wafer is taken out ofthe chamber to process the next manufacturing process.

FIGS. 10A-10I are perspective views of a method for manufacturing asemiconductor device at various stages in accordance with someembodiments of the present disclosure. In some embodiments, thesemiconductor device shown in FIGS. 6A-6E may be intermediate devicesfabricated during processing of an integrated circuit (IC), or a portionthereof, that may include static random access memory (SRAM), logiccircuits, passive components, such as resistors, capacitors, andinductors, and/or active components, such as p-type field effecttransistors (PFETs), n-type FETs (NFETs), multi-gate FETs, metal-oxidesemiconductor field effect transistors (MOSFETs), complementarymetal-oxide semiconductor (CMOS) transistors, bipolar transistors, highvoltage transistors, high frequency transistors, other memory cells, andcombinations thereof.

Reference is made to FIG. 10A. A semiconductor structure is provided.The semiconductor structure includes a substrate 110, a plurality ofsemiconductor fins 116, and an isolation structure 140 laterallysurrounds the semiconductor fins 116. In some embodiments, the formationof the semiconductor fins 116 may be the same or similar to the processshown in FIG. 1B, and, therefore, a detailed description is notrepeated. In some embodiments, the formation of the isolation structure140 may be similar to the process shown in FIGS. 1C-1E. In some otherembodiments, the isolation structure 140 may include filling the trenchby insulator materials such as silicon oxide, silicon nitride, orsilicon oxynitride. The filled trench may have a multi-layer structuresuch as a thermal oxide liner layer with silicon nitride filling thetrench. In some embodiments, the isolation structure 140 may be createdby performing a flowable CVD process to deposit dielectric materials,and using chemical mechanical planarization (CMP) to remove theexcessive dielectric materials.

Then, a dummy dielectric layer 310 is conformally formed to cover thesemiconductor fins 116 and the isolation structures 140. In someembodiments, the dummy dielectric layer 310 may include silicon dioxide,silicon nitride, a high-κ dielectric material or other suitablematerial. In various examples, the dummy dielectric layer 310 may bedeposited by an ALD process, a CVD process, a subatmospheric CVD (SACVD)process, a flowable CVD process, a PVD process, or other suitableprocess. By way of example, the dummy dielectric layer 310 may be usedto prevent damage to the semiconductor fins 116 by subsequent processing(e.g., subsequent formation of the dummy gate structure).

Subsequently, at least one dummy gate structure 320 is formed over thedummy dielectric layer 310, the semiconductor fins 116, and theisolation structures 140. The dummy gate structure 320 includes a dummygate electrode 322, a pad layer 324 formed over the dummy gate electrode322, and a hard mask layer 326 formed over the pad layer 324. In someembodiments, a dummy gate layer (not shown) may be formed over the dummydielectric layer 310, and the pad layer 324 and the hard mask layer 326are formed over the dummy gate layer. The dummy gate layer is thenpatterned using the pad layer 324 and the hard mask layer 326 as masksto form the dummy gate electrode 322. As such, the dummy gate electrode322, the pad layer 324, and the hard mask layer 326 are referred to asthe dummy gate structure 320. In some embodiments, the dummy gateelectrode 322 may be made of polycrystalline-silicon (poly-Si),poly-crystalline silicon-germanium (poly-SiGe), or other suitablematerials. The pad layer 324 may be made of silicon dioxide or othersuitable materials, and the hard mask layer 326 may be made of siliconnitride or other suitable materials.

Reference is made to FIG. 10B. Portions of the dummy dielectric layer310 uncovered by the dummy gate structure 320 are removed to expose thesemiconductor fins 116. Spacer structures 330 are then formed at leaston opposite sides of the dummy gate structure 320. The spacer structures330 may include a seal spacer and a main spacer (not shown). The spacerstructures 330 include one or more dielectric materials, such as siliconoxide, silicon nitride, silicon oxynitride, SiCN, SiCxOyNz, orcombinations thereof. The seal spacers are formed on sidewalls of thedummy gate structure 320 and the main spacers are formed on the sealspacers. The spacer structures 330 can be formed using a depositionmethod, such as plasma enhanced chemical vapor deposition (PECVD),low-pressure chemical vapor deposition (LPCVD), sub-atmospheric chemicalvapor deposition (SACVD), or the like. The formation of the spacerstructures 330 may include blanket forming spacer layers and thenperforming etching operations to remove the horizontal portions of thespacer layers. The remaining vertical portions of the spacer layers formthe spacer structures 330.

Reference is made to FIG. 10C. Epitaxial structures 340 are then formedon portions of the semiconductor fins 116 uncovered by the dummy gatestructure 320 and the spacer structures 330 by performing, for example,a selectively growing process. The epitaxial structures 340 are formedby epitaxially growing a semiconductor material. The semiconductormaterial includes single element semiconductor material, such asgermanium (Ge) or silicon (Si), compound semiconductor materials, suchas gallium arsenide (GaAs) or aluminum gallium arsenide (AlGaAs), orsemiconductor alloy, such as silicon germanium (SiGe) or galliumarsenide phosphide (GaAsP). The epitaxial structures 340 have suitablecrystallographic orientations (e.g., a (100), (110), or (111)crystallographic orientation). In some embodiments, the epitaxialstructures 340 include source/drain epitaxial structures. In someembodiments, where an N-type device is desired, the epitaxial structures340 may include an epitaxially growing silicon phosphorus (SiP) orsilicon carbon (SiC). In some embodiments, where a P-type device isdesired, the epitaxial structures 340 may include an epitaxially growingsilicon germanium (SiGe). The epitaxial processes include CVD depositiontechniques (e.g., vapor-phase epitaxy (VPE) and/or ultra-high vacuum CVD(UHV-CVD)), molecular beam epitaxy, and/or other suitable processes.

Reference is made to FIG. 10D. A contact etch stop layer (CESL) 350 isconformally formed over the structure of FIG. 10C. In some embodiments,the CESL 350 can be a stressed layer or layers. In some embodiments, theCESL 350 has a tensile stress and is formed of Si₃N₄. In some otherembodiments, the CESL 350 includes materials such as oxynitride. In yetsome other embodiments, the CESL 350 may have a composite structureincluding a plurality of layers, such as a silicon nitride layeroverlying a silicon oxide layer. The CESL 350 can be formed using plasmaenhanced CVD (PECVD), however, other suitable methods, such as lowpressure CVD (LPCVD), atomic layer deposition (ALD), and the like, canalso be used.

An interlayer dielectric (ILD) 360 is then formed on the CESL 350. TheILD 360 may be formed by chemical vapor deposition (CVD), high-densityplasma CVD, spin-on, sputtering, or other suitable methods. In someembodiments, the ILD 360 includes silicon oxide. In some otherembodiments, the ILD 360 may include silicon oxy-nitride, siliconnitride, or a low-k material. Then, a planarization process, such as achemical mechanical planarization (CMP) process, is performed toplanarize the ILD 360 and the CESL 350 to expose the dummy gatestructure 320.

Reference is made to FIG. 10E. A replacement gate (RPG) process schemeis employed. In the RPG process scheme, a dummy polysilicon gate (thedummy gate structure 320 of FIG. 10A in this case) is formed in advanceand is replaced later by a metal gate. In some embodiments, the dummygate structure 320 is removed to form a gate trench 332 with the spacerstructures 330 as its sidewalls. In some other embodiments, the dummydielectric layer 310 (see FIG. 10B) is removed as well. The dummy gatestructure 320 (and the dummy dielectric layer 310) may be removed by dryetch, wet etch, or a combination of dry and wet etch. For example, a wetetch process may include exposure to a hydroxide containing solution(e.g., ammonium hydroxide), deionized water, and/or other suitableetchant solutions.

Reference is made to FIG. 10F. A gate dielectric layer 372 is formed inthe gate trench 332. The gate dielectric layer 372 is formed byperforming a bias-induced selectively ALD process, as described ingreater detail below. FIGS. 11A-11F are cross-sectional views takingalong line B-B of FIG. 10F at various stages in accordance with someembodiments of the present disclosure. In some embodiments, the gatedielectric layer 372 in FIG. 10F may be formed in the fabricationapparatus 200 of FIG. 3, and/or the gate dielectric layer 372 is formedby performing the method M1 in FIG. 2. In some embodiments, the timingdiagram of FIG. 5 is also applied to the manufacturing processes inFIGS. 11A-11F. It is noted that the sizes of the precursors shown inFIGS. 11B-11D are illustrated only, and do not limit the scope of theembodiments.

Reference is made to FIGS. 2, 3, and 11A. In operation S12 of the methodM1, a wafer is positioned on a chuck in a fabrication apparatus. Forexample, the wafer (e.g., the structure in FIG. 10E) is positioned on achuck 220 of the fabrication apparatus 200. In some embodiments, avacuum is applied to the chamber 210 to remove oxygen and moistureand/or the temperature is raised to an acceptable level that is suitablefor the ALD deposition.

In operation S14 of the method M1, a bias is applied to the chuck. Forexample, an RF bias is applied to the chuck 220 in the case of FIG. 11A.With the RF bias, since the spacer structure 330 (e.g., a dielectriclayer) has an electrical conductivity lower than that of the substrate110 (e.g., a semiconductor material), charges (i.e., electrons in thiscase) are less movable within the spacer structure 330 (and the ILD360), such that more charges remain in the vicinity of the surface ofthe spacer structure 330 (and the ILD 360) as shown in FIG. 11A.Moreover, since the electrons are lighter than ions, the electrons areeasier to accumulate in the vicinity of the surface of the spacerstructure 330. In some embodiments, the bias may have a power greaterthan about 0 W and equal to or less than about 50 W, e.g., about 20 W.If the power is greater than about 50 W, the gases (e.g., theprecursors/processing gases) in the chamber 210 may be ionized to formplasma, which may bombard the wafer to damage the structure formedthereon.

In some embodiments, the bias applied to the chuck 220 continues a firstperiod T1 as shown in FIG. 5. The bias is applied before precursors arefed into the chamber 210. Once the RF bias is applied to the chuck 220,electrons move to the surfaces of the spacer structure 330 (and the ILD360). Hence, the surfaces of the spacer structure 330 (and the ILD 360)are negative charged in this case.

In operation S16 of the method M1, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and11B. For example, first precursors P1 (e.g., H₂O in this case) are fedinto the chamber 210 from the precursor delivery 240. As shown in FIG.11B, the negative charges (electrons) in the vicinity of the surface ofthe spacer structures 330 repulse the H₂O molecules due to their partialnegative charges (oxygen). The H₂O molecules may be mostly attracted bythe substrate 110, and thus are deposited on the substrate 110 ratherthan on the spacer structures 330 and the ILD 360. As shown in FIG. 11C,the H₂O are mostly absorbed on the surface 112 of the substrate 110.Stated differently, more H₂O molecules are deposited on the substrate110 than on the spacer structures 330 and the ILD 360. In someembodiments, there are still some H₂O are absorbed on the surfaces ofthe dielectric materials (i.e., the spacer structure 330 in this case).

The first precursors P1 are fed into the chamber 210 for a second periodT2 (see FIG. 5). In some embodiments, a third period T3 in FIG. 5 islong enough to charge the spacer structure 330, and a fourth period T4in FIG. 5 is long enough to provide the reaction time of the firstprecursor deposition. Further, during the operations S14 and S16, theplasma source 230 is turned off, such that there is no or negligibleplasma in the chamber 210 when the bias is applied to the chuck 220. Insome other embodiments, the first precursors P1 is plasma, and the firstprecursors P1 are fed into the chamber 210 from the plasma source 230.During this process, the plasma is originated from the plasma source 230and not in the chamber 210, such that a bias with a low power can beapplied to the chuck 220 to perform the selective ALD process.

In operation S18 of the method M1, the bias is turned off, and inoperation S20 of the method M1, the excess first precursors P1 arepurged out of the chamber. Specifically, the first precursors P1 aremostly absorbed to the surface 112 of the substrate 110 during theperiods T2 and T4 (see FIG. 5), and some of the first precursors P1 areabsorbed to the surface of the spacer structures 330. After the fourthperiod T4, the bias is turned off, such that the electrons in thevicinity of the surface of the spacer structure 330 are graduallydisappeared. Then, purging gases enter the chamber 210 to purge theexcess first precursors P1 out of the chamber 210.

In operation S22 of the method M1, second precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and11D. For example, second precursors P2 (e.g., high-k precursor in thiscase) are fed into the chamber 210 from the precursor delivery 240. Asshown in FIG. 11D, the second precursors P2 are attracted by the firstprecursors absorbed on the substrate 110 (—OH in this case). The secondprecursors P2 may be attracted by —OH and thus are mostly deposited onthe substrate 110 rather than on the spacer structure 330. As shown inFIG. 11E, the second precursors P2 are mostly absorbed on the surface112 of the substrate 110 and form a dielectric film 372″ thereon. Asshown in FIG. 11E, the dielectric film 372″ has a first growth rate(i.e., deposition rate) on the substrate 110 greater than a secondgrowth rate on the spacer structure 330 and greater than a third growthrate on the ILD 360.

In some embodiments, the dielectric film 372″ may be a high-k dielectriclayer, such as Al₂O₃, ZrO₂, HfO₂, TiO₂, or other suitable materials.When the monolayer is made of Al₂O₃, the second precursors P2 may beTrimethylaluminum(TMA), Triethylaluminium(TEA), Tetrakis(dimethylamido)aluminum (TDMAA), or other suitable materials. When the monolayer ismade of ZrO₂, the fourth precursors P4 may beTetrakis(dimethylamido)zirconium (TDMAZ), ZrCl₄, or other suitablematerials. When the monolayer is made of HfO₂, the second precursors P2may be Tetrakis(dimethylamido)hafnium (TDMAH), HfCl₄, or other suitablematerials. When the monolayer is made of TiO₂, the second precursors P2may be Tetrakis(dimethylamido)titanium (TDMAT), TiCl₄, or other suitablematerials.

In FIG. 5, the purging of the second precursors P2 maintains for a fifthperiod T5. In some embodiments, a sixth period T6 of FIG. 5 is forneutralizing the surface of the spacer structure 330. In someembodiments, a seventh period T7 of FIG. 5 provides the reaction time ofthe second precursor deposition.

In operation S24 of the method M1, the excess second precursors arepurged out of the chamber. After the operation S24, the dielectric film372″ is mostly formed on the surface 112 of the substrate 110 as shownin FIG. 11E, and this dielectric film 372″ may expose portions of thesurfaces of the spacer structure 330 (and the ILD 360). That is, theselective ALD deposition process results in no or negligible dielectricfilm 372″ deposited on the spacer structure 330 and/or the ILD 360. Forexample, the dielectric film 372″ unintentionally deposited on thespacer structures 330 and/or the ILD 360 may have a thinner thicknessthan that deposited on the substrate 110. Then, the method M1 goes tothe operation S14 to repeat the operations S14-S24 and form anotherdielectric film on the dielectric film 372″. The cycle of the operationsS14-S24 may be repeated many times to form the dielectric layer 372′ inthe gate trench 332, as shown in FIGS. 11F and 10F.

In FIG. 11F, the dielectric layer 372′ has a bottom portion 372 b andsidewall portions 372 s. The bottom portion 372 b is in contact with thesubstrate 110, and the sidewall portions 372 s are in contact with thespacer structures 330. The bottom portion 372 b has a thickness t1greater than a thickness t2 of the sidewall portion 372 s due to thebias-induced selective ALD process. With such configuration, the bottomportion 372 b is thick enough to isolate the semiconductor fin 116 andthe following formed gate electrode, while the sidewall portions 372 sare thin enough to provide large window to deposit the gate metalmaterials. In operation S26 of the method M1, the wafer is taken out ofthe chamber to process the next manufacturing process.

Reference is made to FIG. 10G. At least one metal layer is formed in thegate trench 332 and on the gate dielectric layer 372. Subsequently, achemical mechanical planarization (CMP) process is performed toplanarize the metal layer and the dielectric layer 372′ (see FIG. 10F)to form a metal gate structure 370 in the gate trench 332. The metalgate structure 370 crosses over the semiconductor fins 116. The metalgate structure 370 includes a gate dielectric layer 372 and a metal gateelectrode over the gate dielectric layer 372. The metal gate electrodemay include one or more metal layers 374, e.g., work function metallayer(s) and capping layer(s), a fill metal 376, and/or other suitablelayers. The work function metal layer may include n-type and/or p-typework function metal. Exemplary n-type work function metals include Ti,Ag, TaAl, TaAlC, TiAlN, TaC, TaCN, TaSiN, Mn, Zr, other suitable n-typework function materials, or combinations thereof. Exemplary p-type workfunction metals include TiN, TaN, Ru, Mo, Al, WN, ZrSi₂, MoSi₂, TaSi₂,NiSi₂, WN, other suitable p-type work function materials, orcombinations thereof. The work function metal layer may have multiplelayers. The work function metal layer(s) may be deposited by CVD, PVD,electroplating and/or other suitable process. In some embodiments, themetal gate electrode is a p-type metal gate including a p-type workfunction metal layer. In some embodiments, the capping layer in themetal gate electrodes may include refractory metals and their nitrides(e.g. TiN, TaN, W₂N, TiSiN, TaSiN). The capping layer may be depositedby PVD, CVD, metal-organic chemical vapor deposition (MOCVD) ALD, or thelike. In some embodiments, the fill metal 376 that fills a remainder ofthe gate trench 332 may include tungsten (W). The fill metal 376 may bedeposited by ALD, PVD, CVD, or other suitable process.

Reference is made to FIG. 10H. In some embodiments, the metal gatestructure 370 is etched back to a predetermined level and form anothergate trench 378 thereon. Then, a capping layer 380 is formed over theetched metal gate structure 370 using, for example, a deposition processto deposit a dielectric material over the substrate 110, followed by aCMP process to remove excess dielectric material outside the gatetrenches. In some embodiments, the capping layer 380 includes siliconnitride or other suitable dielectric material. In some embodiments, thecapping layer 380 is formed by performing a bias-induced selective ALDprocess as mentioned above and using the fabrication apparatus 200 ofFIG. 3. Since the formation of the capping layer 380 may be the same orsimilar to the formation of the isolation materials 140′ in FIG. 1C, thedetailed description is not repeated in this respect. The capping layer380 can be used to define self-aligned contact region and thus referredto as SAC structures or a SAC layer.

Reference is made to FIG. 10I. A plurality of source/drain contacts 390are formed over the epitaxial structures 340. For example, a pluralityof the source/drain openings are formed through the ILD 360 and the CESL350 to expose the source/drain epitaxy structures 340, and conductivematerials are filled in the openings and over the source/drain epitaxystructures 340. The excess portions of the conductive materials areremoved to form the source/drain contacts 390. The source/drain contacts390 may be made of tungsten, aluminum, copper, or other suitablematerials.

In FIGS. 10F and 11F, the dielectric layer 372′ is formed by performingthe bias-induced selective ALD process. By providing a bias on the chuck220, the charges have different distributions in different materials.The charges may attract or repulse the precursors to increase ordecrease the corresponding deposition rate. With such configuration, thebottom portion 372 b of the dielectric layer 372′ is thick enough toisolate the semiconductor fin 116 and the following formed gateelectrode, while the sidewall portions 372 s of the dielectric layer372′ are thin enough to provide large window to deposit the gateelectrode. Furthermore, a self-aligned monolayers (SAMs), which mayformed using an additional deposition process and cause defect issues,can be omitted to simplify the manufacturing process.

Further, in FIG. 10H, the capping layer 380 can be formed by performingthe bias-induced selective ALD process. By providing a bias on the chuck220, the charges have different distributions in different materials.The charges may attract or repulse the precursors to increase ordecrease the corresponding deposition rate. In some other embodiments,the planarization process (e.g., CMP) performed after depositing thecapping layer 380 can be omitted when there is a high depositionselectivity between the dielectric layer (i.e., the spacer structure 330and ILD 360) and the conductive layer (i.e., the metal gate structure370). Furthermore, a self-aligned monolayers (SAMs), which may formedusing an additional deposition process and cause defect issues, can beomitted to simplify the manufacturing process.

The dielectric layer 372′ in FIG. 10F may be formed using other biasand/or precursors. FIGS. 12A-12F are cross-sectional views taking alongline B-B of FIG. 10F at various stages in accordance with someembodiments of the present disclosure. Throughout the various views andillustrative embodiments, like reference numbers are used to designatelike elements. The present embodiment may repeat reference numeralsand/or letters used in FIGS. 11A-11F. This repetition is for the purposeof simplicity and clarity and does not in itself dictate a relationshipbetween the various embodiments and/or configurations discussed. In thefollowing embodiments, the structural and material details describedbefore are not repeated hereinafter, and only further information issupplied to perform the semiconductor devices of FIGS. 12A-12F. In someembodiments, the dielectric layer 372′ in FIGS. 12A-12F is performed inthe fabrication apparatus 200 of FIG. 3 and/or using the method M1 inFIG. 2. In some embodiments, the timing diagram of FIG. 5 is alsoapplied to the manufacturing processes in FIGS. 12A-12F. It is notedthat the sizes of the precursors shown in FIGS. 12A-12D are illustratedonly, and do not limit the scope of the embodiments.

Reference is made to FIGS. 2, 3, and 12A. In operation S12 of the methodM1, a wafer is positioned on a chuck of a fabrication apparatus. In someembodiments, the surfaces of the structure (i.e., the substrate 110, thespacer structure 330, and the ILD 360) may be terminated withterminating species TS. In some embodiments, the surfaces of thesubstrate 110, the spacer structure 330, and the ILD 360 initiallycarries the terminating species TS. In some other embodiments, thesurfaces of the substrate 110, the spacer structure 330, and the ILD 360are initially neutral, and a surface treatment (e.g., the cleaningand/or stripping process mentioned above) can be performed on thesurfaces to change or modify the surface termination. In still someother embodiments, H₂O are fed into the chamber 210 to form theterminating species TS on the surfaces.

In operation S14 of the method M1, a bias is applied to the chuck. Thebias is a negative DC bias in the case of FIG. 12A. With the negative DCbias, since the substrate 110 (e.g., a semiconductor material) has anelectrical conductivity higher than that of the spacer structure 330 andthe ILD 360 (e.g., a dielectric layer), charges (i.e., electrons in thiscase) are accumulated within the substrate 110, such that more chargesremain in the vicinity of the surface of the substrate 110 as shown inFIG. 12A. The bias source 270 in FIG. 3 is configured to apply thenegative DC bias to the chuck 220, and the bias may have a power greaterthan about 0 W and equal to or less than about 50 W, e.g., about 20 W.

In some embodiments, the bias applied to the chuck 220 continues a firstperiod T1 as shown in FIG. 5. The bias is applied before precursors arefed into the chamber 210. Once the negative DC bias is applied to thechuck 220, electrons move to the surface 112 of the substrate 110.Hence, the surface of the substrate 110 is negative charged in thiscase.

In operation S16 of the method M1, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and12B. For example, first precursors P1′ (e.g., high-k precursors in thiscase) are fed into the chamber 210 from the precursor delivery 240. Insome embodiments, by controlling the temperature of the chamber 210and/or feeding reaction gases into the chamber 210, a chemical reactionoccurs such that a substituent is removed from the first precursor P1′,and thus the first precursors P1′ become partially positive. The firstprecursors P1′ with partial positive charges are mostly attracted by thesubstrate 110, and thus are mostly deposited on the substrate 110 ratherthan on the mask layer 120. As shown in FIG. 12C, the first precursorsP1′ are mostly absorbed on the surface 112 of the substrate 110. In someembodiments, there are still some first precursors P1′ are absorbed onthe surfaces of the dielectric materials (i.e., the spacer structure 330and/or ILD 360 in this case).

The first precursors P1′ are fed into the chamber 210 for a secondperiod T2 (see FIG. 5). In some embodiments, a third period T3 in FIG. 5is long enough to charge the mask layer 120, and a fourth period T4 inFIG. 5 is long enough to provide the reaction time of the firstprecursor deposition. Further, during the operations S14 and S16, theplasma source 230 is turned off, such that there is no or negligibleplasma in the chamber 210 when the bias is applied to the chuck 220. Insome other embodiments, the first precursors P1′ is plasma, and thefirst precursors P1′ are fed into the chamber 210 from the plasma source230. During this process, the plasma is originated from the plasmasource 230 and not in the chamber 210, such that a bias with a low powercan be applied to the chuck 220 to perform the selective ALD process.

In operation S18 of the method M1, the bias is turned off, and inoperation S20 of the method M1, the excess first precursors are purgedout of the chamber. In operation S22 of the method M1, second precursorsare fed into the chamber of the fabrication apparatus. Reference is madeto FIGS. 3 and 12D. For example, second precursors P2′ (e.g., oxidizerssuch as H₂O vapor, O₃, or O₂ plasma in this case) are fed into thechamber 210 from the precursor delivery 240 or the plasma source 230(for the O₂ plasma oxidizers). As shown in FIG. 12D, the secondprecursors P2′ are attracted by the first precursors absorbed on thesubstrate 110. The second precursors P2′ are likely to be attracted bythe first precursors, and thus more second precursors P2′ are depositedon the surface 112 of the substrate 110 and less second precursors P2′are deposited on the surfaces of the spacer structures 330 (and/or theILD 360). As shown in FIG. 12E, a dielectric film 372″ is formed on thesurfaces of the substrate 110, the spacer structure 330, and/or the ILD360.

In FIG. 5, the purging of the second precursors P2′ maintains for afifth period T5. In some embodiments, a sixth period T6 of FIG. 5 is forneutralizing the surface of the substrate 110. In some embodiments, aseventh period T7 of FIG. 5 provides the reaction time of the secondprecursor deposition.

In operation S24 of the method M1, the excess second precursors arepurged out of the chamber. After the operation S24, a dielectric film372″ is mostly formed on the surface of the substrate 110 as shown inFIG. 12E, and this dielectric film 372″ may expose portions of thesurfaces of the spacer structure 330 (and/or the ILD 360). That is, theselective ALD process results in no or negligible dielectric film 372″deposited on the spacer structure 330 and/or the ILD 360. Then, themethod M1 goes to the operation S14 to repeat the operations S14-S24 andform another dielectric film on the dielectric film 372″. The cycle ofthe operations S14-S24 may be repeated many times to form the dielectriclayer 372′ in the gate trench, as shown in FIGS. 12F and 10F. Inoperation S26 of the method M1, the wafer is taken out of the chamber toprocess the next manufacturing process.

FIGS. 13A-13F are cross-sectional views taking along line B-B of FIG.10F at various stages in accordance with some embodiments of the presentdisclosure. Throughout the various views and illustrative embodiments,like reference numbers are used to designate like elements. The presentembodiment may repeat reference numerals and/or letters used in FIGS.10A-10F. This repetition is for the purpose of simplicity and clarityand does not in itself dictate a relationship between the variousembodiments and/or configurations discussed. In the followingembodiments, the structural and material details described before arenot repeated hereinafter, and only further information is supplied toperform the semiconductor devices of FIGS. 13A-13F. In some embodiments,the dielectric layer 372′ in FIGS. 13A-13F is formed in the fabricationapparatus 200 of FIG. 3 and is performed using the method M2 of FIG. 7.In some embodiments, the timing diagram of FIG. 9 is also applied to themanufacturing processes in FIGS. 13A-13F. It is noted that the sizes ofthe precursors shown in FIGS. 13A-13D are illustrated only, and do notlimit the scope of the embodiments.

Reference is made to FIGS. 3, 7, and 13A. In operation S12 of the methodM2, a wafer is positioned on a chuck of a fabrication apparatus. In someembodiments, the surfaces of the structure (i.e., the substrate 110, thespacer structure 330, and the ILD 360) may be terminated withterminating species TS. In operation S16 of the method M2, firstprecursors are fed into the chamber of the fabrication apparatus.Reference is made to FIGS. 3 and 13A. For example, first precursors P1′(e.g., high-k precursors in this case) are fed into the chamber 210 fromthe precursor delivery 240. The first precursors P1′ are absorbed bothon the surfaces of the substrate 110, the spacer structure 330, and theILD 360 as shown in FIG. 13B.

Reference is made to FIGS. 3, 9, and 13A. In FIG. 9, the firstprecursors P1′ are fed into the chamber 210 for an eighth period T8. Insome embodiments, during the operation S16, the plasma source 230 isturned off, such that there is no or negligible plasma in the chamber210 when the first precursors P1′ are fed into the chamber 210. In someother embodiments, the first precursors P1 is plasma, and the firstprecursors P1 are fed into the chamber 210 from the plasma source 230.In some embodiments, a ninth period T9 in FIG. 9 is long enough toprovide the reaction time of the first precursor deposition.

In operation S20 of the method M2, the excess first precursors arepurged out of the chamber, leaving first precursors absorbed on thesurfaces of the substrate 110, the spacer structure 330, and the ILD 360as shown in FIG. 13B. In operation S14 of the method M2, a bias isapplied to the chuck. The bias is a positive DC bias in the case of FIG.13C. With the positive DC bias, since the substrate 110 (e.g., asemiconductor material) has an electrical conductivity higher than thatof the spacer structure 330 and the ILD 360 (e.g., a dielectric layer),charges (i.e., holes in this case) are accumulated within the substrate110, such that more charges remain in the vicinity of the surface 112 ofthe substrate 110 as shown in FIG. 13B. The bias source 270 in FIG. 3 isconfigured to apply the positive DC bias to the chuck 220, and the biasmay have a power greater than about 0 W and equal to or less than about50 W, e.g., about 20 W.

In some embodiments, the bias applied to the chuck 220 continues a tenthperiod T10 as shown in FIG. 9. The bias is applied before the secondprecursors P2′ (see FIG. 13D) are fed into the chamber 210. Once thepositive DC bias is applied to the chuck 220, holes move to the surface112 of the substrate 110. Hence, the surface 112 of the substrate 110 ispositive charged in this case.

In operation S22 of the method M2, second precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and13D. For example, second precursors P2′ (e.g., H₂O in this case) are fedinto the chamber 210 from the precursor delivery 240. The positivecharges (holes) in the vicinity of the surface of the substrate 110attract the H₂O molecules due to their partial negative charges(oxygen). The H₂O molecules may be mostly attracted by the substrate110, and thus are mostly deposited on the substrate 110 rather than onthe spacer structure 330 (and/or the ILD 360). As shown in FIG. 13E, theH₂O molecules are mostly absorbed on the surface 112 of the substrate110 to form the dielectric film 372″. In some embodiments, there arestill some H₂O molecules are absorbed on the surfaces of the dielectricmaterials (i.e., the spacer structure 330 and the ILD 360 in this case).

Reference is made to FIG. 9. After the bias applied to the chuck 220 isturned on and before the bias is turned off, the second precursors P2′are fed into the chamber 210 for an eleventh period T11. In someembodiments, the eleventh period T11 is shorter than the tenth periodT10 by multiple times. Further, the bias is turned off after the feedingof the second precursor P2′ is stopped. A twelfth period T12 is betweenthe beginning of the bias supply and the beginning of the secondprecursor feeding, and a thirteenth period T13 is between the finish ofthe second precursor feeding and the finish of the bias supply. In someembodiments, the twelfth period T12 is long enough to charge thesubstrate 110, and the thirteenth period T13 is long enough to providethe reaction time of the second precursor deposition.

In operation S18 of the method M2, the bias is turned off, and inoperation S24 of the method M2, the excess second precursors are purgedout of the chamber. After the operation S24, a dielectric film 372″ ismostly formed on the surface 112 of the substrate 110 as shown in FIG.13E, and this dielectric film 372″ may expose portions of the surfacesof the spacer structure 330 (and/or the ILD 360). That is, the selectiveALD process results in no or negligible dielectric film 372″ depositedon the spacer structure 330 and the ILD 360. Then, the method M2 goes tothe operation S16 to repeat the operations S16-S24 and form anotherdielectric film on the dielectric film 372″. The cycle of the operationsS16-S24 may be repeated many times to form the dielectric layer 372′ inthe gate trench 332, as shown in FIGS. 13F and 10F. In operation S26 ofthe method M2, the wafer is taken out of the chamber to process the nextmanufacturing process.

FIG. 14 is a perspective view of a semiconductor device according tosome embodiments. In some embodiments, after the formation of thedielectric layer 372′ (e.g., the processes shown in FIGS. 11F, 12F, and13F), an isotropic etching process is performed to the dielectric layer372′ to remove the sidewall portions 372 s of the dielectric layer 372′and also thin down the bottom portion 372 b of the dielectric layer372′. Then, the metal layer 374 and the fill metal 376 are formed in thegate trench 332 to form the metal gate structure 370. In FIG. 14, themetal layer 374 is in contact with the spacer structure 330 and the gatedielectric layer 372. Since other structural and manufacturing detailsof the semiconductor device in FIG. 14 are similar to the semiconductordevice in FIG. 10I, detailed description is not repeated hereinafter.

FIGS. 15A-15K are cross-sectional views of a method for manufacturing asemiconductor structure at various stages in accordance with someembodiments of the present disclosure. In some embodiments, thesemiconductor structure shown in FIGS. 15A-15K may be intermediatedevices fabricated during processing of an integrated circuit (IC), or aportion thereof, that may include static random access memory (SRAM),logic circuits, passive components, such as resistors, capacitors, andinductors, and/or active components, such as p-type field effecttransistors (PFETs), n-type FETs (NFETs), multi-gate FETs, metal-oxidesemiconductor field effect transistors (MOSFETs), complementarymetal-oxide semiconductor (CMOS) transistors, bipolar transistors, highvoltage transistors, high frequency transistors, other memory cells, andcombinations thereof.

Reference is made to FIG. 15A. A substrate 410 is provided. Thesemiconductor substrate 410 may be or include a bulk semiconductor, asemiconductor-on-insulator (SOI) substrate, or the like, which may bedoped (e.g., with a p-type or an n-type dopant) or undoped. In someembodiments, the semiconductor material of the semiconductor substrate410 may include elemental semiconductor like silicon (Si) and germanium(Ge); a compound semiconductor; an alloy semiconductor; or a combinationthereof.

Various devices may be on the semiconductor substrate 410. For example,the semiconductor substrate 410 may include Field Effect Transistors(FETs), such as Fin FETs (FinFETs), planar FETs, vertical gate allaround FETs (VGAA FETs), or the like; diodes; capacitors; inductors; andother devices. Devices may be formed wholly within the semiconductorsubstrate 410, in a portion of the semiconductor substrate 410 and aportion of one or more overlying layers, and/or wholly in one or moreoverlying layers, for example. Processing described herein may be usedto form and/or to interconnect the devices to form an integratedcircuit. The integrated circuit can be any circuit, such as for anApplication Specific Integrated Circuit (ASIC), a processor, memory, orother circuit.

A first dielectric layer 420 is formed above the semiconductor substrate410. The first dielectric layer 420 may be directly on the semiconductorsubstrate 410, or any number of other layers may be disposed between thefirst dielectric layer 420 and the semiconductor substrate 410. Forexample, the first dielectric layer 420 may be or include an Inter-MetalDielectric (IMD) or an Inter-Layer Dielectric (ILD). The firstdielectric layer 420, for example, may be or include a low-k dielectrichaving a k-value less than about 4.0, such as about 2.0 or even less. Insome examples, the first dielectric layer 420 includes silicon oxide,phosphosilicate glass (PSG), borophosphosilicate glass (BPSG),fluorosilicate glass (FSG), SiO_(x)C_(y), silicon carbon material, acompound thereof, a composite thereof, or combinations thereof.

A conductive feature 430 is in and/or through the first dielectric layer420. The conductive feature 430 may be or include a conductive lineand/or a conductive via, a gate structure of a transistor, or a contactto a gate structure of a transistor and/or to a source/drain region of atransistor. In some embodiments, the first dielectric layer 420 is anIMD, and the conductive feature 430 may include a conductive line and/ora conductive via (collectively or individually, “interconnectstructure”). The interconnect structure may be formed by forming anopening and/or recess through and/or in the IMD, for example, using adamascene process. Some examples of forming an interconnect structureare described further below, although other processes and interconnectstructures may be implemented. In other examples, the first dielectriclayer 420 may include an ILD, and the conductive feature 430 may includea gate electrode (e.g., tungsten, cobalt, etc.) in the ILD formed usinga replacement gate process, for example. In some other embodiments, thefirst dielectric layer 420 may be an ILD, and the conductive feature 430may include a contact. The contact may be formed by forming an openingthrough the ILD to, for example, a gate electrode and/or source/drainregion of a transistor formed on the semiconductor substrate 410. Thecontact can include an adhesion layer (e.g., Ti, etc.), a barrier layer(e.g., TiN, etc.) on the adhesion layer, and a conductive fill material(e.g., tungsten, cobalt, etc.) on the barrier layer. The contact canalso be made of a less diffusive metal like tungsten, Mo, or Ru withouta barrier layer.

A second dielectric layer 440 is formed above the first dielectric layer420 and the conductive feature 430. For example, the second dielectriclayer 440 may be or include an IMD. The second dielectric layer 440 isdeposited on the top surfaces of the first dielectric layer 420 and theconductive feature 430. The second dielectric layer 440, for example,may be or include a low-k dielectric having a k-value less than about4.0, such as about 2.0 or even less. In some examples, the seconddielectric layer 440 includes silicon oxide, PSG, BPSG, FSG,SiO_(x)C_(y), silicon carbon material, a compound thereof, a compositethereof, or combinations thereof. The second dielectric layer 440 may bedeposited using a CVD, such as PECVD or Flowable CVD (FCVD); spin-oncoating; or another deposition technique. In some examples, a ChemicalMechanical Planarization (CMP) or another planarization process may beperformed to planarize the top surface of second dielectric layer 440.

At least one via 450 is formed in the second dielectric layer 440. Insome embodiments, at least one opening is formed in the seconddielectric layer 440, conductive materials are filled in the opening,and a planarization process is performed to remove the excess conductivematerials. Hence, the via 450 is formed and in contact with theconductive feature 430. The via 450 may be made of tungsten, aluminum,copper, or other suitable materials.

Then, an etching stop layer (ESL) 460 (see FIG. 15H) is formed above thesecond dielectric layer 440. The ESL 460 is formed by performing abias-induced selective ALD process, as described in greater detailbelow. In some embodiments, the ESL 460 is formed in the fabricationapparatus 200 of FIG. 3 and/or by performing the method M1 in FIG. 2.Also, the time table in FIG. 5 may be applied to the formation of theESL 460. It is noted that the sizes of the precursors shown in FIGS.15C-15E are illustrated only, and do not limit the scope of theembodiments.

Reference is made to FIGS. 2, 3, and 15B. In operation S12 of the methodM1, a wafer is positioned on a chuck in a fabrication apparatus. Forexample, the wafer (e.g., the structure in FIG. 15A) is positioned on achuck 220 of the fabrication apparatus 200. In some embodiments, avacuum is applied to the chamber 210 to remove oxygen and moistureand/or the temperature is raised to an acceptable level that is suitablefor the ALD deposition.

In operation S14 of the method M1, a bias is applied to the chuck. Forexample, a negative DC bias is applied to the chuck 220 in the case ofFIG. 15B. With the DC bias, since the via 450 (e.g., a conductivematerial) has an electrical conductivity higher than that of the seconddielectric layer 440 (e.g., a dielectric material), charges (i.e.,electrons in this case) are accumulated within the via 450, such thatmore charges remain in the vicinity of the surface of the via 450 asshown in FIG. 15B. In some embodiments, the bias may have a powergreater than about 0 W and equal to or less than about 50 W, e.g., about20 W. If the power is greater than about 50 W, the gases (e.g., theprecursors/processing gases) in the chamber 210 may be ionized to formplasma, which may bombard the wafer to damage the structure formedthereon.

In some embodiments, the bias applied to the chuck 220 continues a firstperiod T1 as shown in FIG. 5. The bias is applied before precursors arefed into the chamber 210. Once the negative DC bias is applied to thechuck 220, electrons move to the surfaces of the via 450. Hence, thesurface of the via 450 is negative charged in this case.

In operation S16 of the method M1, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and15C. For example, first precursors P1 (e.g., H₂O in this case) are fedinto the chamber 210 from the precursor delivery 240. As shown in FIG.15C, the negative charges (electrons) in the vicinity of the surface ofthe via 450 repulse the H₂O molecules due to their partial negativecharges (oxygen). The H₂O molecules may be mostly attracted by thesecond dielectric layer 440, and thus are deposited on the seconddielectric layer 440 rather than on the via 450. As shown in FIG. 15D,the H₂O are mostly absorbed on the surface 442 of the second dielectriclayer 440. In some embodiments, there are still some H₂O are absorbed onthe surfaces of the via 450.

The first precursors P1 are fed into the chamber 210 for a second periodT2 (see FIG. 5). In some embodiments, a third period T3 in FIG. 5 islong enough to charge the via 450, and a fourth period T4 in FIG. 5 islong enough to provide the reaction time of the first precursordeposition. Further, during the operations S14 and S16, the plasmasource 230 is turned off, such that there is no or negligible plasma inthe chamber 210 when the bias is applied to the chuck 220. In some otherembodiments, the first precursors P1 is plasma, and the first precursorsP1 are fed into the chamber 210 from the plasma source 230. During thisprocess, the plasma is originated from the plasma source 230 and not inthe chamber 210, such that a bias with a low power can be applied to thechuck 220 to perform the selective ALD process.

In operation S18 of the method M1, the bias is turned off, and inoperation S20 of the method M1, the excess first precursors P1 arepurged out of the chamber. Specifically, the first precursors P1 aremostly absorbed to the surface 442 of the second dielectric layer 440during the periods T2 and T4 (see FIG. 5), and some of the firstprecursors P1 are absorbed to the surface of the via 450. After thefourth period T4, the bias is turned off, such that the electrons in thevicinity of the surface of the via 450 are gradually disappeared. Then,purging gases enter the chamber 210 to purge the excess first precursorsP1 out of the chamber 210.

In operation S22 of the method M1, second precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and15E. For example, second precursors P2 (e.g., high-k precursor in thiscase) are fed into the chamber 210 from the precursor delivery 240. Asshown in FIG. 15E, the second precursors P2 are attracted by the firstprecursors absorbed on the second dielectric layer 440 (—OH in thiscase). The second precursors may be attracted by —OH and thus are mostlydeposited on the second dielectric layer 440 rather than on the via 450.As shown in FIG. 15F, the second precursors P2 are mostly absorbed onthe surface 442 of the second dielectric layer 440 and form a dielectricfilm 460″ thereon. In some embodiments, the dielectric film 460″ may bea high-k dielectric layer.

In FIG. 5, the purging of the second precursors P2 maintains for a fifthperiod T5. In some embodiments, a sixth period T6 of FIG. 5 is forneutralizing the surface of the via 450. In some embodiments, a seventhperiod T7 of FIG. 5 provides the reaction time of the second precursordeposition.

In operation S24 of the method M1, the excess second precursors arepurged out of the chamber. After the operation S24, a dielectric film460″ is mostly formed on the surface 442 of the second dielectric layer440 as shown in FIG. 15F, and this dielectric film 460″ may exposeportions of the surfaces of the via 450. That is, the selective ALDprocess results in no or negligible dielectric film 460″ deposited onthe via 450. Then, the method M1 goes to the operation S14 to repeat theoperations S14-S24 and form another dielectric film on the dielectricfilm 460″. The cycle of the operations S14-S24 may be repeated manytimes to form the dielectric layer 460′ above the second dielectriclayer 440, as shown in FIG. 15G. In FIG. 15G, the dielectric layer 460′includes a thick portion 460 a directly above the second dielectriclayer 440 and a thin portion 460 b directly above the via 450. Athickness t3 of the thick portion 460 a is greater than a thickness t4of the thin portion 460 b.

Reference is made to FIG. 15H. An etching process is performed on thedielectric layer 460′ to remove the thin portion 460 b and thin down thethick portion 460 a of FIG. 15G. Hence, the ESL 460 is formed. The ESL460 exposes the via 450 while covers the second dielectric layer 440. Insome embodiments, a sidewall of the ESL 460 is substantially alignedwith a sidewall of the via 450.

Reference is made to FIG. 15I. A third dielectric layer 470 is formedabove the ESL 460. For example, the third dielectric layer 470 may be orinclude an IMD. The third dielectric layer 470 is deposited on the topsurface of the ESL 460 and in contact with the via 450. The thirddielectric layer 470, for example, may be or include a low-k dielectrichaving a k-value less than about 4.0, such as about 2.0 or even less. Insome examples, the third dielectric layer 470 includes silicon oxide,PSG, BPSG, FSG, SiO_(x)C_(y), silicon carbon material, a compoundthereof, a composite thereof, or combinations thereof. The thirddielectric layer 470 may be deposited using a CVD, such as PECVD orFlowable CVD (FCVD); spin-on coating; or another deposition technique.In some examples, a Chemical Mechanical Planarization (CMP) or anotherplanarization process may be performed to planarize the top surface ofthird dielectric layer 470.

Reference is made to FIG. 15J. An opening 472 is formed in the thirddielectric layer 470. The opening 472 may formed using photolithographyand etch processes, such as in a dual damascene process. For example, aphoto resist can be formed on the third dielectric layer 470, such as byusing spin-on coating, and patterned with a pattern corresponding to theopening 472 by exposing the photo resist to light using an appropriatephotomask. Exposed or unexposed portions of the photo resist may then beremoved depending on whether a positive or negative resist is used. Thepattern of the photo resist may then be transferred to the thirddielectric layer 470, such as by using a suitable etch process, whichforms the opening 472 in the third dielectric layer 470. The etchprocess may include a reactive ion etch (RIE), neutral beam etch (NBE),inductive coupled plasma (ICP) etch, the like, or a combination thereof.The etch process may be anisotropic. The ESL 460 is used as an etch stopfor the etch process, such that the opening 472 does not expose thesecond dielectric layer 440 but the via 450. Subsequently, the photoresist is removed in an ashing or wet strip process, for example.

Reference is made to FIG. 15K. A conductive line 480 is formed in theopening 472. For example, a conductive material fills in the opening 472(see FIG. 15J). The conductive material at least includes metal element,e.g., copper (Cu). The conductive material may include other suitablematerials such as Ru, W, Ti, Al, Co, or combinations thereof. Then, aplanarization process (e.g., CMP) is performed after the formation ofthe conductive material to remove the excess portions of the conductivematerial outside the opening 472, thus exposing the top surface of thethird dielectric layer 470 and achieving a planarized surface. Theportion of the conductive material in the opening 472 is referred to asthe conductive line 480.

In FIG. 15K, the ESL 460 has an opening 462 directly above the via 450.The opening 462 has a side surface 464 substantially coterminous with asidewall 452 of the via 450. A portion of the conductive line 480 is inthe opening 462 and in contact with the via 450. The conductive line 480is spaced apart from the second dielectric layer 440. The ESL 460 issandwiched between the second dielectric layer 440 and the conductiveline 480, and the conductive line 480 is in contact with the sidesurface 464 of the ESL 460 and a top surface of the ESL 460. Further, aninterface 475 between the third dielectric layer 470 and the conductiveline 480 is set back from the side surface 464 of the ESL 460. Theconductive line 480 and the second dielectric layer 440 are respectivelyin contact with opposite surfaces of the ESL 460. The sidewall 452 ofthe via 450 is non-parallel with the side surface 464 of the ESL 460.

In FIG. 15G, the dielectric layer 460′ is formed by performing thebias-induced selective ALD process. By providing a bias on the chuck220, the charges have different distributions in different materials.The charges may attract or repulse the precursors to increase ordecrease the corresponding deposition rate. In some other embodiments,the etching process shown in FIG. 15H can be omitted when there is ahigh deposition selectivity between the dielectric layer (i.e., thesecond dielectric layer 440) and the conductive layer (i.e., the via450). Furthermore, a self-aligned monolayers (SAMs), which may formedusing an additional deposition process and cause defect issues, can beomitted to simplify the manufacturing process.

The dielectric layer 460′ in FIG. 15G may be formed using other biasand/or precursors. FIGS. 16A-16G are cross-sectional views a method formanufacturing a semiconductor structure at various stages in accordancewith some embodiments of the present disclosure. Throughout the variousviews and illustrative embodiments, like reference numbers are used todesignate like elements. The present embodiment may repeat referencenumerals and/or letters used in FIGS. 15A-15K. This repetition is forthe purpose of simplicity and clarity and does not in itself dictate arelationship between the various embodiments and/or configurationsdiscussed. In the following embodiments, the structural and materialdetails described before are not repeated hereinafter, and only furtherinformation is supplied to perform the semiconductor devices of FIGS.16A-16G. In some embodiments, the dielectric layer 460′ in FIGS. 16A-16Fis formed in the fabrication apparatus 200 of FIG. 3 and/or byperforming the method M1 of FIG. 2. In some embodiments, the time tableof FIG. 5 is also applied to the manufacturing processes in FIGS.16A-16F. It is noted that the sizes of the precursors shown in FIGS.16B-16D are illustrated only, and do not limit the scope of theembodiments.

Reference is made to FIGS. 2, 3, and 16A. In operation S12 of the methodM1, a wafer is positioned on a chuck of a fabrication apparatus. Forexample, a positive DC bias is applied to the chuck 220 in the case ofFIG. 16A. With the DC bias, since the via 450 (e.g., a conductivematerial) has an electrical conductivity higher than that of the seconddielectric layer 440 (e.g., a dielectric material), charges (i.e., holesin this case) are accumulated within the via 450, such that more chargesremain in the vicinity of the surface of the via 450 as shown in FIG.16A. In some embodiments, the bias may have a power greater than about 0W and equal to or less than about 50 W, e.g., about 20 W. If the poweris greater than about 50 W, the gases (e.g., the precursors/processinggases) in the chamber 210 may be ionized to form plasma, which maybombard the wafer to damage the structure formed thereon.

In some embodiments, the bias applied to the chuck 220 continues a firstperiod T1 as shown in FIG. 5. The bias is applied before precursors arefed into the chamber 210. Once the positive DC bias is applied to thechuck 220, holes move to the surface of the via 450. Hence, the surfaceof the via 450 is positive charged in this case.

In operation S16 of the method M1, first precursors are fed into thechamber of the fabrication apparatus. Reference is made to FIGS. 3 and16B. For example, first precursors P1′ (e.g., high-k precursors in thiscase) are fed into the chamber 210 from the precursor delivery 240. Insome embodiments, by controlling the temperature of the chamber 210and/or feeding reaction gases into the chamber 210, a chemical reactionoccurs such that a substituent is removed from the first precursor P1′,and thus the first precursors P1′ are partially positive. The firstprecursors P1′ with partial positive charges are mostly repulsed by thevia 450, and thus are mostly deposited on the second dielectric layer440 rather than on the via 450. As shown in FIG. 16C, the firstprecursors P1′ are mostly absorbed on the surface 442 of the seconddielectric layer 440. In some embodiments, there are still some firstprecursors P1′ are absorbed on the surfaces of the via 450.

The first precursors P1′ are fed into the chamber 210 for a secondperiod T2 (see FIG. 5). In some embodiments, a third period T3 in FIG. 5is long enough to charge the via 450, and a fourth period T4 in FIG. 5is long enough to provide the reaction time of the first precursordeposition. Further, during the operations S14 and S16, the plasmasource 230 is turned off, such that there is no or negligible plasma inthe chamber 210 when the bias is applied to the chuck 220. In some otherembodiments, the first precursors P1′ is plasma, and the firstprecursors P1′ are fed into the chamber 210 from the plasma source 230.

In operation S18 of the method M1, the bias is turned off, and inoperation S20 of the method M1, the excess first precursors are purgedout of the chamber. In operation S22 of the method M1, second precursorsare fed into the chamber of the fabrication apparatus. Reference is madeto FIGS. 3 and 16D. For example, second precursors P2′ (e.g., oxidizerssuch as H₂O vapor, O₃, or O₂ plasma in this case) are fed into thechamber 210 from the precursor delivery 240 or the plasma source 230(for the O₂ plasma oxidizers). As shown in FIG. 16D, the secondprecursors P2′ are attracted by the first precursors P1′ absorbed on thesecond dielectric layer 440. The second precursors P2′ are likely to beattracted by the first precursors, and thus more second precursors P2′are deposited on the surfaces 442 of the second dielectric layer 440 andless second precursors P2′ are deposited on the surface of the via 450.As shown in FIG. 16E, a dielectric film 460″ is formed on the surfacesof the second dielectric layer 440 and the via 450.

In FIG. 5, the purging of the second precursors P2′ maintains for afifth period T5. In some embodiments, ae sixth period T6 of FIG. 5 isfor neutralizing the surface of the via 450. In some embodiments, aseventh period T7 of FIG. 5 provides the reaction time of the secondprecursor deposition.

In operation S24 of the method M1, the excess second precursors arepurged out of the chamber. After the operation S24, a dielectric film460″ is mostly formed on the surface 442 of the second dielectric layer440 as shown in FIG. 16E, and this dielectric film 460″ may exposeportions of the surfaces of the via 450. That is, the selective ALDprocess results in no or negligible dielectric film 460″ deposited onthe via 450. Then, the method M1 goes to the operation S14 to repeat theoperations S14-S24 and form another dielectric film on the dielectricfilm 460″. The cycle of the operations S14-S24 may be repeated manytimes to form the dielectric layer 460′ above the second dielectriclayer 440, as shown in FIG. 16F. In operation S26 of the method M1, thewafer is taken out of the chamber to process the next manufacturingprocess.

Then, the processes in FIGS. 15H-15K are performed to form thesemiconductor structure as shown in FIG. 16G. Since the structure andformation of the semiconductor structure in FIG. 16G may be the same orsimilar to the formation of the semiconductor structure in FIGS.15H-15K, the detailed description is not repeated in this respect.

Based on the above discussions, it can be seen that the presentdisclosure offers advantages. It is understood, however, that otherembodiments may offer additional advantages, and not all advantages arenecessarily disclosed herein, and that no particular advantage isrequired for all embodiments. One advantage is that a selective ALDprocess can be performed by applying a DC and/or RF bias. Anotheradvantage is that the bias-induced selective ALD process is an indirectinducement process, and an SAMs or other additional layer forselectively deposition, which may damage the structure formed on thewafer or include additional process(es), can be omitted. Furthermore,the bias-induced selective ALD process does not complicate themanufacturing process for forming the semiconductor devices and/orsemiconductor structures.

According to some embodiments, a method includes forming a dummy gatestructure over a wafer. Gate spacers are formed on either side of thedummy gate structure. The dummy gate structure is removed to form a gatetrench between the gate spacers. A gate dielectric layer is formed inthe gate trench. A gate electrode is formed over the gate dielectriclayer. Forming the gate dielectric layer includes applying a first biasto the wafer. With the first bias turned on, first precursors are fed tothe wafer. The first bias is turned off. After turning off the firstbias, second precursors are fed to the wafer.

According to some embodiments, a method includes forming a mask layerabove a substrate. The substrate is patterned by using the mask layer asa mask to form a trench in the substrate. An isolation structure isformed in the trench, including feeding first precursors to thesubstrate. A bias is applied to the substrate after feeding the firstprecursors. With the bias turned on, second precursors are fed to thesubstrate. Feeding the first precursors, applying the bias, and feedingthe second precursors are repeated.

According to some embodiments, a device includes a conductive feature, afirst dielectric layer, a via, an etch stop layer (ESL), a seconddielectric layer, and a conductive line. The first dielectric layer isabove the conductive feature. The via is in the first dielectric layerand above the conductive feature. The ESL is above the first dielectriclayer. A side surface of the ESL is coterminous with a sidewall of thevia. The second dielectric layer is above the ESL. The conductive linein the second dielectric layer and over the via. The conductive line isin contact with the side surface of the ESL and a top surface of theESL.

The foregoing outlines features of several embodiments so that thoseskilled in the art may better understand the aspects of the presentdisclosure. Those skilled in the art should appreciate that they mayreadily use the present disclosure as a basis for designing or modifyingother processes and structures for carrying out the same purposes and/orachieving the same advantages of the embodiments introduced herein.Those skilled in the art should also realize that such equivalentconstructions do not depart from the spirit and scope of the presentdisclosure, and that they may make various changes, substitutions, andalterations herein without departing from the spirit and scope of thepresent disclosure.

What is claimed is:
 1. A method comprising: forming a mask layer above asubstrate; patterning the substrate by using the mask layer as a mask toform a trench in the substrate; and forming an isolation structure inthe trench, comprising: feeding first precursors to the substrate;applying a bias to the substrate after feeding the first precursors;with the bias turned on, feeding second precursors to the substrate; andrepeating feeding the first precursors, applying the bias, and feedingthe second precursors.
 2. The method of claim 1, wherein the bias is apositive bias.
 3. The method of claim 1, wherein the bias is a negativebias.
 4. The method of claim 1, wherein the first precursors are siliconprecursors.
 5. The method of claim 1, wherein the second precursors areH₂O.
 6. The method of claim 1, wherein a power of the bias is greaterthan about 0 W and equal to or less than about 50 W.
 7. The method ofclaim 1, wherein the bias is turned off after stopping feeding thesecond precursors.
 8. The method of claim 1, further comprising:performing a chemical-mechanical polishing process on the isolationstructure.
 9. The method of claim 8, further comprising: recessing theisolation structure such that fins of the substrate protrude above therecessed isolation structure.
 10. A method comprising: forming a masklayer above a substrate; patterning the substrate by using the masklayer as a mask to form a trench in the substrate; and forming anisolation structure in the trench by using an atomic layer deposition(ALD) process, the ALD process comprises one or more repetitions of anALD cycle, the ALD cycle comprising: applying a bias to the substrate;during applying the bias to the substrate, feeding first precursors tothe substrate such that a deposition rate of the first precursors overthe substrate is greater than a deposition rate of the first precursorsover the mask layer; turning off the bias; and after turning off thebias, feeding second precursors to the substrate.
 11. The method ofclaim 10, wherein the bias is less than about 50 W.
 12. The method ofclaim 10, wherein the first precursors are H₂O.
 13. The method of claim10, wherein the second precursors are silicon precursors.
 14. The methodof claim 10, further comprising: stopping feeding the first precursorsbefore turning off the bias.
 15. The method of claim 10, wherein thebias is an RF bias.
 16. The method of claim 10, wherein applying thebias to the substrate is performed such that more electrons areaccumulated on a surface of the mask layer than on a surface of thesubstrate.
 17. The method of claim 10, further comprising: formingterminating species on the substrate and the mask layer before formingthe isolation structure, the terminating species comprising —OH.
 18. Amethod comprising: forming a mask layer above a substrate; patterningthe substrate by using the mask layer as a mask to form a trench in thesubstrate; and forming an isolation structure in the trench by using anatomic layer deposition (ALD) process, the ALD process comprises one ormore repetitions of an ALD cycle, the ALD cycle comprising: accumulatingmore electrons on a surface of the mask layer than on a surface of thesubstrate; after accumulating more electrons on the surface of the masklayer than on the surface of the substrate, feeding first precursorsover the substrate such that a deposition rate of the first precursorsover the substrate is greater than a deposition rate of the firstprecursors over the mask layer; and feeding second precursors over thesubstrate to form silicon oxide.
 19. The method of claim 18, wherein thesecond precursors are fed in a bias-free condition.
 20. The method ofclaim 18, wherein the first precursors are H₂O, and the secondprecursors are silicon precursors.